EP0660860B1 - Ensemble ou jeu d'encres de couleurs differentes et ensemble d'instruments d'ecriture - Google Patents

Ensemble ou jeu d'encres de couleurs differentes et ensemble d'instruments d'ecriture Download PDF

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Publication number
EP0660860B1
EP0660860B1 EP93922214A EP93922214A EP0660860B1 EP 0660860 B1 EP0660860 B1 EP 0660860B1 EP 93922214 A EP93922214 A EP 93922214A EP 93922214 A EP93922214 A EP 93922214A EP 0660860 B1 EP0660860 B1 EP 0660860B1
Authority
EP
European Patent Office
Prior art keywords
ink
reducible
assembly
inks
basic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP93922214A
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German (de)
English (en)
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EP0660860A1 (fr
EP0660860A4 (fr
Inventor
Jorge Cancellieri
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gillette Co LLC
Original Assignee
Gillette Co LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gillette Co LLC filed Critical Gillette Co LLC
Publication of EP0660860A1 publication Critical patent/EP0660860A1/fr
Publication of EP0660860A4 publication Critical patent/EP0660860A4/fr
Application granted granted Critical
Publication of EP0660860B1 publication Critical patent/EP0660860B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43K—IMPLEMENTS FOR WRITING OR DRAWING
    • B43K27/00—Multiple-point writing implements, e.g. multicolour; Combinations of writing implements

Definitions

  • the present invention relates to colored inks reacting therebetween, for producing colors different from those of any of them.
  • magic inks as, for example, the product called “Magicolor” (Registered Trademark) developed by Sylvapen Distrib. S.A.C.I.F and other similar products based on the same principle.
  • the eraser includes a sodium sulphite solution as reducing agent; although other reducing agents have also been proposed and tested, such as sodium thiosulphite, hydrosulphite and bisulphite, as well as the corresponding potassium salts, and even some organic reducing agents, such as formaldehyde or hydroquinone.
  • magic inks also known as “turnable inks”
  • turnable inks include an assembly of inks sensitive to a reducing agent (called “reducible ink” henceforward), carried by in writing and/or drawing instruments, while the reducing agent is contained in, and dispensed from, another similar instrument, whose lines or strokes are uncolored. I.e., the path of the instrument bearing the writing agent on paper, for example, is only distinguished at the regions covered by reducible inks, revealed by the appearance of the colors corresponding to the reduced forms of said inks.
  • the color combination afforded by conventional "magic inks" or multiple color inks is limited by the number of reducible inks; i.e. by the number of writing and/or drawing instruments (henceforward also called “color units”).
  • each color unit gives two different colors: one corresponding to the unreduced form and the other to the reduced form of each ink.
  • the color spectrum which may be obtained with conventional multiple color inks only comprises colors of each ink and colors of the reduced form thereof, without any chromatic addition from the instrument carrying the reducing agent (from now on also called “reducing unit").
  • the invention relates to multiple color inks and corresponding writing and/or drawing instruments, wherein the reducing agent is associated to, or included into, a non reducible ink.
  • the so-called “eraser” unit is colored with permanent coloring, opposite to conventional "magic inks", wherein the "eraser” is colorless.
  • One object of the invention is an assembly or set of drawing or writing inks, of different colors or of multiple colors changing their color by reduction, and at least a non reducible ink, the formulation of which includes a reducing agent for said reducible inks, the ink carrying the reducing agent, for producing a different and unexpected chromatic effect with each reduced ink, different from the chromatic effect produced in the absence of the reducing reaction.
  • Another object of the invention is a writing or drawing instrument assembly with multiple color strokes or characters, each of which comprises a reservoir containing a different color reducible ink, additionally at least one of the instruments in the assembly contains a non reducible ink comprising a reducing agent for the inks of the remaining instruments, the non reducible ink producing, with the reduced inks, a chromatic effect different from that produced when two of the non reduced reducible inks are mixed or overlapped on a substrate such as paper, glass or metal sheet, or on a plastic surface.
  • a further object of the invention is an assembly or set of multiple color inks which, apart from the reducible inks and from the non reducible ink bearing the reducing agent, may also include the reducing agent diluted into a colorless vehicle.
  • a further object of the invention is an assembly comprised by two inks: a reducible ink containing a coloring agent or coloring agent mixture which changes its color when reduced, and a non reducible ink containing a reducing agent for said reducible ink, and further comprising a non reducible coloring agent or a mixture of coloring agents reacting with the reducible ink, for producing a chromatic effect from the reduction color and non reducible coloring agent mixture.
  • An additional object of the invention is an assembly or set of drawing or writing instruments each of which includes a different color reducible ink; further, at least one of said instruments including a non reducible ink carrying the reducing agent for the reducible inks.
  • the assembly may include an instrument including the reducing agent diluted into a colorless vehicle, the non reducible ink producing an unexpected chromatic effect with the reduced inks, different from that produced with the non reduced inks, when at least one of the non reduced inks are mixed or overlapped.
  • Reduction color is the color resulting from the mixture of reducing ink and reducible ink.
  • Reducible ink is a colored solution changing its color when contacted with suitable reducing substances under the application conditions.
  • Reducing ink is a colored solution containing a reducing agent or material, capable of reducing the reducible ink, under the application conditions.
  • Coloring substances and coloring agents are used, indistinctly, for individualizing the organic colored substances capable of giving a permanent and perceivable color in solution.
  • Reference numeral 10 in Figure 2 corresponds to strokes or lines made with one ink of the assembly of conventional multiple color inks, crossed by clearer lines 11a, due to the reduction of ink 10.
  • the path or travel of the instrument carrying the reducing agent is only partly revealed by a single area; the reduction of ink 10 in the region or zone 11a.
  • reference 10 corresponds to lines with reducible ink 10, as that of Figure 2, crossed by a region or zone 11b, corresponding to the chromatic combination of the color of the reduced form of the ink 10 and the color of the non reducible ink, containing the reducing agent for ink 10.
  • the passage of the reducing agent is apparent due to the formation of said region or zone 11b and due to lines 12, because of the color of the non reducible ink, in accordance with the invention.
  • the assembly or set of multiple color inks according to the invention allows obtaining a broader polychromatic effect in what concerns the color range and the possibility of obtaining different color lines, figures, blots, etc., as compared to known magic inks. It has been already indicated that the instant invention adds to colors of reducible inks and colors of reduced reducible inks (B), non reducible ink color (A) and colors resulting from the optical composition (combination) of (A) + (B) to the color spectrum of conventional multiple color inks.
  • chromatic effects depend, in quality and quantity, on the nature of the coloring agent formulated with the non reducible ink, as well as on the coloring agents formulated in reducible inks; i.e. the diversity and strength of colors depends on the choice of the coloring agents of both types (reducible and non reducible).
  • the instant invention is not specifically related to a family or kind of coloring agents or of any other type; any of known reducible coloring agents applied to known multiple color inks may be used in the instant invention.
  • the following reducible coloring substances recorded in the Colour Index (C.I.) are preferred: Basic red 18; Basic red 19; Food red 7; Basic yellow 28; Acid yellow 9; Acid blue 93:2 Basic blue 9; Basic green 1; Basic violet 10; Acid orange 8 and mixtures thereof.
  • a possible non reducible ink formulation comprises, for example: 8-10% sodium sulphite, 15% triethanolamine (TEA) and non reducible coloring agents comprising 3.0% Direct blue 86; or 2.0% Solvent green 7; or 0.6% Acid red 52 or 2.0% Acid blue 1 (percentages by weight); or mixtures thereof.
  • non reducible coloring agents generally any stable or solid coloring agent in the same formulation along with the reducing agent and complying with the conditions of the invention for non reducible coloring agents may be used; preferably coloring substances recorded in the C.I. such as: Direct blue 86; Solvent green 7; Acid red 52 and Acid blue 1, and mixtures thereof.
  • the reducing agent common to multiple color inks is sodium sulphite, used in the formulation called “eraser” or “magic line” (Sylvapen).
  • sodium sulphite used in the formulation called "eraser” or "magic line” (Sylvapen).
  • other reducing agents such as bisulphites, thiosulphites, are also useful in the instant invention, sodium sulphite and alkaline metal hydrosulphites are preferred, including organic reducing agents such as hydroquinone and formaldehyde.
  • Sodium bisulphite is preferred in the case of the instant invention.
  • the selection of the reducing agent depends on the redox potential of the coloring agents of the reducible inks as well as of the ink bearing the reducing agent.
  • the selection of the coloring substances and the reducing agent depends on the combination between the redox potential of the reducing agent and the redox potentials of reducible coloring substances and the coloring substance formulated in the ink carrying the reducing agent (eraser).
  • Preparation of reducible and non reducible inks is simple, known, and available to those skilled in the art. It comprises formulation of the selected coloring substances in solutions of suitable solvents with pH adjusting additives, e.g. bases for creating a solvent medium with a suitable pH for the development of the reducible ink reaction; suitable bases are, for example, diethanol and triethanolamine, specially triethanolamine.
  • pH adjusting additives e.g. bases for creating a solvent medium with a suitable pH for the development of the reducible ink reaction
  • suitable bases are, for example, diethanol and triethanolamine, specially triethanolamine.
  • the following example corresponds to a set of inks comprised by a reducing ink (A) and a reducible ink (B) formulated in accordance with the instant invention, included with illustrative purposes, not limiting the scope of the invention.
  • Reducing ink (A) (fluorescent yellow color) Reducible ink (B) (blue color) %w/w %w/w Sodium sulphite 10.0 Basic violet 10 0.50 Solvent green 7 2.0 Basic blue 9 0.25 Chloroacetamide 0.1 Basic green 1 0.25 Glycerin 12.0 Chloroacetamide 0.1 Triethanolamine 85% 18.0 Glycerin 6.0 Propyleneglycol 9.0 Deionized water c.s.p. 100.0 Deionized water c.s.p. 100.0
  • the mixture or the portions of the reducible ink covered with the reducing ink take unexpectedly a brilliant brown color - reduction color - instead of the expected violet produced with the conventional "eraser” (colorless), formulation of which corresponds to that indicated as (A) but without the coloring agent (Solvent green 7).
  • the assembly or set of multiple color inks according to the invention may be used, as well as those known inks called "magic inks" for making multiple color figures, drawings, legends, etc. on paper, cardboard, cloth, by means of conventional writing or drawing instruments, such as known fiber or ball pencils or pens.
  • writing and drawing instruments are available in assemblies or sets comprised by several different reducible color instruments or units and at least one unit or instrument dispensing simultaneously the reducing agent and the non reducible coloring substance, formulated in the same non reducible ink.
  • assemblies or kits including two or more non reducible color units, apart from the plurality of reducible color units, each of which dispenses the reducing agent, i.e. more than one color unit in which the reducing agent is formulated with a different non reducible coloring substance; optionally, said assemblies or sets may include further a conventional instrument dispensing only the reducing agent. Any of these two alternatives broadens the chromatic possibilities of writing and drawing inks and instruments of the instant invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Pens And Brushes (AREA)
  • Mechanical Pencils And Projecting And Retracting Systems Therefor, And Multi-System Writing Instruments (AREA)

Claims (12)

  1. Ensemble ou jeu d'encres de différentes couleurs, utilisé pour composer des figures, des légendes, des dessins, polychromatiques, dans lequel ledit ensemble comporte une pluralité d'encres réductibles dont la couleur change par réduction et au moins une encre non réductible incluant un agent colorant et un agent réducteur pour ladite pluralité d'encres réductibles; ladite encre qui porte l'agent réducteur générant un effet chromatique lorsqu'elle est mise en contact avec chaque encre réductible, en donnant une couleur différente de celle de l'effet chromatique produit lorsque l'on mélange une encre non réduite avec une autre encre non réduite.
  2. Ensemble comme revendiqué dans la revendication 1, dans lequel l'encre non réductible est une solution d'une substance colorante choisie dans l'Index des Couleurs: bleu direct 86, vert à solvant 7, rouge acide 52 et bleu acide 1, et leurs mélanges.
  3. Ensemble comme revendiqué dans la revendication 1, dans lequel des encres réductibles sont des solutions colorantes choisies parmi: Rouge basique 18 Bleu acide 93:2 Rouge basique 14 Bleu basique 9 Rouge basique 49 Vert basique 4 Rouge alimentaire 7 Vert basique 1 Jaune basique 28 Violet basique 10 Jaune acide 9 Orange acide 8
    et leurs mélanges.
  4. Ensemble comme revendiqué dans la revendication 1, dans lequel l'agent réducteur est un sulfite, un bisulfite, un thiosulfite ou un hydrosulfite d'un métal alcalin.
  5. Ensemble comme revendiqué dans la revendication 4, dans lequel l'agent réducteur est le sulfite de sodium.
  6. Ensemble comme revendiqué dans la revendication 1, dans lequel chaque encre inclut une base telle que la triéthanolamine.
  7. Ensemble pour l'écriture ou le dessin comme revendiqué dans la revendication 1, caractérisé par le fait que l'agent réducteur est un agent réducteur organique tel que formaldéhyde ou hydroquinone.
  8. Ensemble pour l'écriture ou le dessin en couleurs multiples dans lequel ledit ensemble comporte une pluralité d'instruments d'écriture ou de dessin dont chacun comporte un réservoir pour l'une des encres réductibles et un autre réservoir pour l'encre non réductible, conformément à l'ensemble défini dans la revendication 1.
  9. Ensemble pour l'écriture ou le dessin comme revendiqué dans la revendication 8, dans lequel ledit instrument est un instrument en fibres pour le dessin ou l'écriture.
  10. Ensemble ou jeu de deux encres, comportant:
    a) une encre réductible
    b) une encre non réductible contenant un matériau colorant et un agent réducteur réagissant avec l'encre réductible pour produire un effet chromatique dérivé du mélange de la couleur résultant de la réduction et de l'agent coloré.
  11. Ensemble de deux encres comme revendiqué dans la revendication 10, dans lequel l'encre non réductible est une solution d'une substance colorante choisie parmi le bleu direct 86, le vert à solvant 7, le rouge acide 52 et le bleu acide 1 et leurs mélanges (Index des Couleurs).
  12. Ensemble de deux encres comme revendiqué dans la revendication 10, dans lequel l'encre réductible est une solution aqueuse d'un matériau colorant choisi parmi Rouge basique 18 Bleu acide 93:2 Rouge basique 14 Bleu basique 9 Rouge basique 49 Vert basique 4 Rouge alimentaire 7 Vert basique 1 Jaune basique 28 Violet basique 10 Jaune acide 9 Orange acide 8
    et leurs mélanges.
EP93922214A 1992-09-18 1993-09-16 Ensemble ou jeu d'encres de couleurs differentes et ensemble d'instruments d'ecriture Expired - Lifetime EP0660860B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AR32320992 1992-09-18
AR32320992 1992-09-18
PCT/US1993/008755 WO1994006872A1 (fr) 1992-09-18 1993-09-16 Ensemble ou jeu d'encres de couleurs differentes et ensemble d'instruments d'ecriture

Publications (3)

Publication Number Publication Date
EP0660860A1 EP0660860A1 (fr) 1995-07-05
EP0660860A4 EP0660860A4 (fr) 1996-09-18
EP0660860B1 true EP0660860B1 (fr) 1998-07-08

Family

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Family Applications (1)

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EP93922214A Expired - Lifetime EP0660860B1 (fr) 1992-09-18 1993-09-16 Ensemble ou jeu d'encres de couleurs differentes et ensemble d'instruments d'ecriture

Country Status (10)

Country Link
US (1) US5549742A (fr)
EP (1) EP0660860B1 (fr)
JP (1) JP3758670B2 (fr)
AU (1) AU5129493A (fr)
BR (1) BR9204277A (fr)
DE (1) DE69319606T2 (fr)
MX (1) MX9206283A (fr)
SG (1) SG47891A1 (fr)
UY (1) UY23504A1 (fr)
WO (1) WO1994006872A1 (fr)

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Also Published As

Publication number Publication date
EP0660860A1 (fr) 1995-07-05
DE69319606T2 (de) 1999-02-25
AU5129493A (en) 1994-04-12
BR9204277A (pt) 1994-03-22
MX9206283A (es) 1994-03-31
JP3758670B2 (ja) 2006-03-22
JPH08501508A (ja) 1996-02-20
UY23504A1 (es) 1993-04-26
SG47891A1 (en) 1998-04-17
WO1994006872A1 (fr) 1994-03-31
EP0660860A4 (fr) 1996-09-18
US5549742A (en) 1996-08-27
DE69319606D1 (de) 1998-08-13

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